This invention relates to a process for the separation of a hydrocarbon bearing gas stream containing significant quantities of components more volatile than methane (e.g., hydrogen, nitrogen, etc.) into two fractions: a first fraction containing predominantly methane and the more volatile components, and a second fraction containing the recovered desirable ethane/ethylene and heavier hydrocarbon components.
Ethylene, ethane, propylene, propane, and/or heavier hydrocarbons can be recovered from a variety of gases, such as natural gas, refinery gas, and synthetic gas streams obtained from other hydrocarbon materials such as coal, crude oil, naphtha, oil shale, tar sands, and lignite. Hydrocarbon bearing gas typically contains components more volatile than methane (e.g., hydrogen, nitrogen, etc.) and often unsaturated hydrocarbons (e.g., ethylene, propylene, etc.) and aromatic hydrocarbons (e.g., benzene, toluene, etc.) in addition to methane, ethane, and hydrocarbons of higher molecular weight such as propane, butane, and pentane. Sulfur-containing gases and carbon dioxide are also sometimes present.
The present invention is generally concerned with the recovery of ethylene, ethane, and heavier (C2+) hydrocarbons from such gas streams. Recent changes in ethylene demand have created increased markets for ethylene and derivative products. In addition, fluctuations in the prices of both natural gas and its natural gas liquid (NGL) constituents have increased the value of ethane and heavier components as liquid products. These market conditions have resulted in the demand for processes which can provide high ethylene and ethane recovery and more efficient recovery of all these products. Available processes for separating these materials include those based upon cooling and refrigeration of gas, oil absorption, and refrigerated oil absorption. Additionally, cryogenic processes have become popular because of the availability of economical equipment that produces power while simultaneously expanding and extracting heat from the gas being processed. Depending upon the pressure of the gas source, the richness (ethane, ethylene, and heavier hydrocarbons content) of the gas, and the desired end products, each of these processes or a combination thereof may be employed.
The cryogenic expansion process is now generally preferred for natural gas liquids recovery because it provides maximum simplicity with ease of startup, operating flexibility, good efficiency, safety, and good reliability. U.S. Pat. Nos. 3,292,380; 4,061,481; 4,140,504; 4,157,904; 4,171,964; 4,185,978; 4,251,249; 4,278,457; 4,519,824; 4,617,039; 4,687,499; 4,689,063; 4,690,702; 4,854,955; 4,869,740; 4,889,545; 5,275,005; 5,555,748; 5,566,554; 5,568,737; 5,771,712; 5,799,507; 5,881,569; 5,890,378; 5,983,664; 6,182,469; 6,578,379; 6,712,880; 6,915,662; 7,191,617; 7,219,513; reissue U.S. Pat. No. 33,408; and co-pending application Ser. Nos. 11/430,412; 11/839,693; 11/971,491; 12/206,230; 12/689,616; 12/717,394; 12/750,862; 12/772,472; 12/781,259; 12/868,993; 12/869,007; and 12/869,139 describe relevant processes (although the description of the present invention in some cases is based on different processing conditions than those described in the cited U.S. patents and applications).
In a typical cryogenic expansion recovery process, a feed gas stream under pressure is cooled by heat exchange with other streams of the process and/or external sources of refrigeration such as a propane compression-refrigeration system. As the gas is cooled, liquids may be condensed and collected in one or more separators as high-pressure liquids containing some of the desired C2+ components. Depending on the richness of the gas and the amount of liquids formed, the high-pressure liquids may be expanded to a lower pressure and fractionated. The vaporization occurring during expansion of the liquids results in further cooling of the stream. Under some conditions, pre-cooling the high pressure liquids prior to the expansion may be desirable in order to further lower the temperature resulting from the expansion. The expanded stream, comprising a mixture of liquid and vapor, is fractionated in a distillation (demethanizer or deethanizer) column. In the column, the expansion cooled stream(s) is (are) distilled to separate residual methane, hydrogen, nitrogen, and other volatile gases as overhead vapor from the desired C2 components, C3 components, and heavier hydrocarbon components as bottom liquid product, or to separate residual methane, C2 components, hydrogen, nitrogen, and other volatile gases as overhead vapor from the desired C3 components and heavier hydrocarbon components as bottom liquid product.
If the feed gas is not totally condensed (typically it is not), the vapor remaining from the partial condensation can be passed through a work expansion machine or engine, or an expansion valve, to a lower pressure at which additional liquids are condensed as a result of further cooling of the stream. The pressure after expansion is essentially the same as the pressure at which the distillation column is operated. The combined vapor-liquid phases resulting from the expansion are supplied as feed to the column.
In the ideal operation of such a separation process, the residue gas leaving the process will contain substantially all of the methane and more volatile components in the feed gas with essentially none of the heavier hydrocarbon components, and the bottoms fraction leaving the demethanizer will contain substantially all of the heavier hydrocarbon components with essentially no methane or more volatile components. In practice, however, this ideal situation is not obtained because the conventional demethanizer is operated largely as a stripping column. The methane product of the process, therefore, typically comprises vapors leaving the top fractionation stage of the column, together with vapors not subjected to any rectification step. Considerable losses of ethylene and ethane occur because the top liquid feed contains substantial quantities of C2+ components and heavier hydrocarbon components, resulting in corresponding equilibrium quantities of C2+ components in the vapors leaving the top fractionation stage of the demethanizer. This problem is exacerbated if the gas stream(s) being processed contain relatively large quantities of components more volatile than methane (e.g., hydrogen, nitrogen, etc.) because the volatile vapors rising up the column strip C2+ components from the liquids flowing downward. The loss of these desirable C2+ components could be significantly reduced if the rising vapors could be brought into contact with a significant quantity of liquid (reflux) capable of absorbing the C2+ components from the vapors.
A number of processes have been developed to use a cold liquid that is predominantly methane as the reflux stream to contact the rising vapors in a rectification section in the distillation column. Typical process schemes of this type are disclosed in U.S. Pat. Nos. 4,889,545; 5,568,737; and 5,881,569, and in Mowrey, E. Ross, “Efficient, High Recovery of Liquids from Natural Gas Utilizing a High Pressure Absorber”, Proceedings of the Eighty-First Annual Convention of the Gas Processors Association, Dallas, Tex., Mar. 11-13, 2002. Unfortunately, these processes require the use of a compressor to provide the motive force for recycling the reflux stream to the demethanizer, adding to both the capital cost and the operating cost of facilities using these processes. In addition, the cold methane reflux creates temperatures within the distillation column that are −112° F. [−80° C.] and colder. Many gas streams of this type contain significant quantities of nitrous oxides (NOX) at times, which can accumulate in cold sections of a processing plant as NOX gums (commonly referred to as “blue ice”) at temperatures lower than this. “Blue ice” can become explosive upon warming, and has been identified as the cause of a number of deflagrations and/or explosions in processing plants.
Other processes have been developed that use a heavy (C4-C10 typically) hydrocarbon absorbent stream to reflux the distillation column. Examples of processes of this type are U.S. Pat. Nos. 4,318,723; 5,546,764; 7,273,542; and 7,714,180. While such processes generally operate at temperatures warm enough to avoid concerns about “blue ice”, the absorbent stream is typically produced from the distillation column bottoms stream, with the result that any aromatic hydrocarbons present in the feed gas will concentrate in the distillation column. Aromatic hydrocarbons such as benzene can freeze solid at normal processing temperatures, causing frequent disruptions in the processing plant.
In accordance with the present invention, it has been found that ethane recovery in excess of 88% can be obtained without requiring any temperatures to be lower than −112° F. [−80° C.]. The present invention is particularly advantageous when processing feed gases containing more than 10 mole % of components more volatile than methane.
In the following explanation of the above figures, tables are provided summarizing flow rates calculated for representative process conditions. In the tables appearing herein, the values for flow rates (in moles per hour) have been rounded to the nearest whole number for convenience. The total stream rates shown in the tables include all non-hydrocarbon components and hence are generally larger than the sum of the stream flow rates for the hydrocarbon components. Temperatures indicated are approximate values rounded to the nearest degree. It should also be noted that the process design calculations performed for the purpose of comparing the processes depicted in the figures are based on the assumption of no heat leak from (or to) the surroundings to (or from) the process. The quality of commercially available insulating materials makes this a very reasonable assumption and one that is typically made by those skilled in the art.
For convenience, process parameters are reported in both the traditional British units and in the units of the Système International d'Unitès (SI). The molar flow rates given in the tables may be interpreted as either pound moles per hour or kilogram moles per hour. The energy consumptions reported as horsepower (HP) and/or thousand British Thermal Units per hour (MBTU/Hr) correspond to the stated molar flow rates in pound moles per hour. The energy consumptions reported as kilowatts (kW) correspond to the stated molar flow rates in kilogram moles per hour.